CH677857B5 - - Google Patents

Abstract

Diallylamine compounds may be polymerized to water-soluble, linear, high-molecular weight polymers having low residual monomer content by the use of cationic azo initiators and phosphorous acid or a derivative thereof as regulator. The polymers are useful as pre- or after-treatment agents for anionic dyeings on textile substrates.

Description

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description

EP 0 140 309 describes a process for the preparation of copolymers of monoallylamine and dialylamine, in which special initiators are used which have an azo group and a group with cationic nitrogen in the same molecule.

In J. Macromol-Sci.-Chem., A 10 (5), pp. 857-873 (1976) on page 863 states that initiators such as azobis-isobutyramidinium hydrochloride are suitable for the polymerization of triallylamine to give solid, crosslinked polymers. It is striking that the initiators mentioned there were not used for the production of homopolymers of diallylamine. Experiments have shown that the polymerization leads to solid, gel-like polymers under comparable conditions.

EP 95 233 describes polymerizations of monoallylamines, the process for the preparation being characterized in that initiators as described in EP 140 309 are used and the polymerization is carried out in an acidic medium, for example phosphoric acid.

It has now been found that water-soluble, in particular linear, higher molecular weight homopolymers of diallylamine can be obtained by polymerization using initiators which contain an azo group and at least one group with cationic nitrogen in the same molecule, if regulators, such as phosphoric acid or derivatives of it, such as Mono- or diesters, preferably mono- or dialkyl esters, such as methyl or ethyl esters, are used.

The present invention therefore relates to a process for producing a water-soluble homopolymer of diallylamine, the homopolymer thus prepared and its use for the pretreatment and / or aftertreatment of dyeings with dyes containing anionic groups, such as with textile materials containing direct * or reactive dyes on hydroxyl groups or nitrogen atoms -en as well as the pretreated and / or post-treated textile materials.

A diallylamine is advantageously a monomer of the formula in which R 1 and R 2 independently of one another are hydrogen or a methyl group, R 3 is hydrogen and R 4 is hydrogen, an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted benzyl group or cyclohexyl or R 3 and R4 together with the nitrogen atom form a piperidine or morpholine ring and X © denotes an anion, in particular an HSO40, -SO4 © or CI ©.

Examples of substituted alkyl groups are hydroxy and cyanoethyl, amino, alkylamino and dialkylaminoalkyl groups, each having 1 to 5 carbon atoms and preferably 1 to 3 carbon atoms in the alkyl radical.

Initiators which contain an azo group and a group with cationic nitrogen are those of the formula

(R5-N = N-R6) ®X © II,

in which R5 and R6 independently of one another represent an alkyl, aryl, alkaryl, aralkyl, cyanoalkyl, cyano-aryl, cyanoalkaryl or cyanoaralkyl group or R5 and R6 together form an alkylene, alkylalkylene or arylalkylene group, where R5 and / or R6 carries a substituent with a cationized nitrogen atom, and X © represents an anion. Initiators of the formula mentioned are preferred in which at least one of the radicals R5 and R6 represents a cationized aminoalkyl, aminoaryl, amidinoalkyl, amidinoaryl, aminoalkaryl, aminoaralkyl, amidinoaikaryl, amidinoaralkyl, cyanoaminoalkyl or cyanaminoalkaryl group.

Initiators include described in European patent specifications 95 233 and 145 220; preferred initiators are 2,2-azo-bis (2-amidinopropane) dihydrochloride, 2,2-azo-bis (2-amidinobutane) dihydrochloride, 2,2-azo-bis (N-phenylamidinopropane) dihydrochloride, 2, 2-azo-bis (N, N-dimethylamidino-propane) dihydrochloride, 2,2-azo-bis (N-hydroxyethylamidinopropane) dihydrochloride and 2,2-azo-bis [2- (imidazolinyl) propane] dihydrochloride.

These initiators are used in amounts of 0.2-10% by weight, based on the weight of the monomers used. Amounts of 1 to 5% are preferably used.

Phosphorous acid is particularly suitable as a regulator. It is used in amounts of 0.01 to 0.5 mol

CHp = C - CH2

I,

r2 x ©

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equivalents, preferably 0.025 to 0.2 molar equivalents based on the weight of the monomers dial-lyl compound used.

The polymerization is carried out according to generally known methods and proceeds, for example, in such a way that an acidic solution of a diallylamine salt, advantageously at a pH of 1.5-5 and preferably 2-3, and the phosphorous acid is heated while passing a stream of nitrogen (temperature from 50 to 80 ° C), the initiator is added in small portions and the polymerization is completed at the boiling point. The acidic solution is advantageously a mineral acidic solution such as e.g. a hydrochloric acid or sulfuric acid solution, advantageously an acidic solution. The polyamine base can, if desired, be added by adding a base such as e.g. Sodium hydroxide to be released to the cooled solution. The polymers can be isolated by generally known methods. The homopolymers can have the recurring structural units of the formulas III and IV:

R2

• CH2— C - C— CH2-

ch2 ch2 / \

r3 r4

X ©

or

III

ch2 - c

R1, R2 -1

ch2 r3 xr4

c-

I.

ch2

X ©

-J IV

or in the form of the free base.

In this way, homopolymers of diallylamine are obtained which are preferably linear and tend, if at all, to extremely little crosslinking; in addition, they are also very readily soluble in water as a free base, in contrast to crosslinked diallyl polymers, which are highly viscous and are also very poorly soluble in water as salts; as hydrochloride in aqueous solution with a concentration of 55-65% by weight, they have a viscosity of 500 m Pa s (Brookfield, spindle No. 4, 100 rpm) to 10,000 m Pa s (Brookfield, spindle No. 4, 10 rpm). As a 20-30% solution, the free polyamine base has a viscosity of 100 m Pa s (Brookfield, spindle No. 3, 100 rpm) to 2000 m Pa s (Brookfield, spindle No. 4, 100 rpm). The polymers obtained also have an extremely low residual monomer content, advantageously less than 3 percent by weight.

The water-soluble homopolymers of diallylamine have a variety of uses as polybasic polymers. A preferred use is the aftertreatment of dyeings or prints which are obtained with dyes containing anionic groups, such as with direct or reactive dyes on textile materials which contain hydroxyl groups or nitrogen atoms. Such textiles are natural or synthetic polyamide fibers such as wool, silk, nylon and cellulose or regenerated cellulose fibers. The preferred substrate is cotton. The textiles mentioned can preferably be dyed or printed with dyes as described in DOS 3 525 104.

The polymer according to the invention is used according to known methods as an aqueous solution in the exhaust process or the textile material is impregnated with such a solution. The amounts to be used can vary and are determined by the type of coloring and the depth of color. In the case of dyeing with direct dyes, amounts of 0.5-6%, advantageously 2-4%, based on the substrate, are used in the exhaust process; in the padding process, amounts of 5-60 g / l, advantageously 20-40 g / l, are used . In the case of reactive dyeing, amounts of 0.5-6%, advantageously 0.5-3% and especially 0.5-1% are used.

A preferred aftertreatment by the exhaust process is such that the dyed textile material is immersed in a fixing liquor which, in addition to the homopolymer of diallylamine, contains sodium chloride and a sufficient amount of a base to adjust the pH to about 12-13 at room temperature and heated this liquor to 60 ° C. The liquor remains at this temperature for about 15 minutes, after which the material is rinsed and neutralized.

Such a post-treatment significantly improves wet fastness, such as water, wash and sweat fastness, for direct dyeing. An advantage of this aftertreatment compared to known aftertreatment methods is the permanence of the effects achieved, with minimal change in nuance and little influence on the light fastness. In the case of reactive dyeing, the hydrolysed dye components, which do not have to be washed out, are fixed in a washable manner. In addition, the perborate fastness is improved.

Another use of the water-soluble homopolymers of diallylamine is the pretreatment of textile materials which contain hydroxyl groups or nitrogen atoms in order to improve the subsequent dyeing with the direct or reactive dyes mentioned. In this way, more intense colorations are obtained, and in particular it becomes possible to use reactive dyes even in acid pH

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Freeze area. Amounts of 0.5-15%, advantageously 0.5-6% and preferably 2-6%, based on the substrate, are used for such a pretreatment.

The invention is explained with the aid of the following examples, in which temperatures are given in degrees Celsius and percentages in percent by weight.

Manufacturing examples

1) 193.9 parts of diallylamine hydrochloride solution with a concentration of 68.85% are heated to 8.2 ° with 8.2 parts of phosphorous acid while continuously passing a stream of nitrogen. A solution of 3.5 parts of 2,2'-azobis (2-amidinopropane) dihydrochloride in 19.8 parts of water is then metered in uniformly over the course of 19 hours. The mixture is stirred at 65 ° for 21 hours and then heated to about 95-100 °, stirred for 2 hours and cooled.

The 59.2% polymer hydrochloride has a viscosity of 1540 m Pa s (Brookfield, spindle No. 4, 50 rpm). The free polyamine base can be released by stirring in 142 parts of a 30% strength aqueous sodium hydroxide solution. 367 parts of polyamine solution with a concentration of 26.4% are obtained. The viscosity is 630 m Pa s (Brookfield, spindle 4,100 rpm).

2) If the procedure is as in Example 1, but the amount of phosphorous acid is reduced to 4.1 parts, a polymer hydrochloride of 60.3% with a viscosity of 2950 mPas is obtained (Brookfield, spindle No. 4, 20 rpm). If this product is diluted with 215 parts of water and the polymer base is released with 265.2 parts of a 30% aqueous sodium hydroxide solution, a 21% solution with a viscosity of 225 mPas is obtained (Brookfield, spindle No. 3,100 rpm).

Application examples

A. A dyeing with 3% of the dye Cl-Direct Blue 251 240% on a 100% cotton knitwear is subsequently fixed in order to improve the wet fastness:

Fleet ratio 1:20,

Aftertreatment from a fresh bath with 4% of the compound according to Preparation Example 1 (product of the free polyamine base with 25-27% free amine content, amount of active substance of the polyamine base, based on the product used 1-1.2%).

The fixing liquor also contains 5 g / l sodium chloride and is adjusted to a pH of approx. 12-13 with 2 ml / l sodium hydroxide solution at 36 ° Bé.

Fixation begins at room temperature in the liquor (approx. 20 °) and increases to 60 °, it remains at this temperature for 15 minutes, rinsing and neutralizing with acetic acid.

B. A 100% cotton dyeing with 3% of the dye of Example 2 from DOS 3 247 605 is fixed according to Example A with 3% of the product of the free polyamine base from Preparation Example 1. The result is excellent permanent wet fastness with minimal influence on the change in nuance.

C. A dyeing with 3% of the dye CI Drimaren Reactiv Blau 79 is rinsed after the dyeing and shortened soaped. Without aftertreatment, insufficient wet fastness properties, poor per borate and wash fastness properties are obtained.

An aftertreatment according to Example A with amounts of the product from Preparation Example 1 of between 0.5 and 3%, depending on the depth of color, results in improved wet and wash fastnesses compared with dyeings that have not been aftertreated, and the perborate fastness is also improved.

D. A fabric made of 100% cotton is treated with 3% of the auxiliary according to Example 1, based on the dry weight of the substrate, for 20 minutes at a pH of 10-12 and at 60 ° in the exhaust process. The tissue is then rinsed, neutralized and finished using known methods. The fabric pretreated in this way is dyed using the shortened pad-batch process.

For this purpose, the fabric is padded with 27 g / l Cl Reactive Red 171 and acetic acid at a pH of 4.5 up to a liquor absorption of 80-90%; the tissue is rolled up, wrapped in plastic sheeting and left for 30 minutes. The fabric is then rinsed warm and cold and finished using known methods. Despite the short dwell time, a deeper dyeing with good fastness properties is obtained compared to a same dyeing without pretreatment. The padding can also be carried out in the presence of a non-inogenic net agent. Equally good results are obtained if, instead of Cl Reactive Red 171, 5 g / l Cl Reactive Red 5 or 5 g / l Cl Reactive Blue 163 are used.

Claims (13)

Claims 1. A process for the preparation of water-soluble diallylamine homopolymers, characterized in that a diallylamine or an acid addition salt thereof is polymerized in the presence of an initiator which contains one azo group and at least one group with cationic nitrogen in the molecule, and a regulator and, if appropriate, a corresponding polymer converted into the form of the free polyamine base in the form of a salt by treatment with a base. 5 5 10th 15 20th 25th 30th 35 40 45 50 55 CH 677 857G A3 2. The method according to claim 1, characterized in that one of a monomer of the formula Î1 CH2 = c - CH, R, \ / X "(I) ch2 = ç - ch2 r4 r2 wherein R 1 and R 2, independently of one another, represent hydrogen or a methyl group, R3 for hydrogen and R4 represents hydrogen, an optionally substituted alkyl group with 1-5 carbon atoms, an optionally substituted benzyl group or cyclohexyl and X "denotes an anion, polymerized and optionally a corresponding polymer in the form of a salt by treatment with a base in the form of the free polyamine base. 3. The method according to claim 2, characterized in that diallylamine is polymerized in the form of a salt of inorganic or organic acids and the polyamine base is released by treatment with sodium hydroxide. 4. The method according to claim 3, characterized in that initiators of the formula (R5-N = N-R6) + X- (II) wherein R5 and R6 independently of one another represent an alkyl, aryl, alkaryl, aralkyl, cyanoalkyl, cyano-aryl, cyanoalkaryl or cyanoaralkyl group or R5 and R6 together form an alkylene, alkylalkylene or arylalkylene group, wherein R5 and / or R6 carries a substituent with a cationized nitrogen atom, and X- represents an anion, are used. 5. The method according to claim 4, characterized in that at least one of the radicals R5 and R6 is a cationized aminoalkyl, aminoaryl, amidinoalkyl, amidinoaryl, aminoalkaryl, aminoaralkyl, amidinoalkaryl, amidinoaralkyl, cyanaminoalkyl or cyanaminoalkaryl group. 6. The method according to any one of claims 1 to 5, characterized in that the regulator used is phosphorous acid or a mono- or diester thereof. 7. The method according to claim 6, characterized in that one uses phosphorous acid in an amount of 0.01 to 0.5 molar equivalent, preferably 0.025 to 0.2 molar equivalent, based on the amount of diallylamine. 8. The method according to any one of claims 1 to 7, characterized in that diallylamine is polymerized in the form of a salt of inorganic or organic acids and the polyamine base is released by treatment with sodium hydroxide. 9. The homopolymers produced by the process according to one of claims 1 to 8. 10. Homopolymer of diallylamine in the form of the hydrochloride according to claim 9, whose solution in water with a concentration of 55 wt .-% to 65 wt .-% has a viscosity of 500 mPa s (Brookfield, Spindel, No. 4,100 UmP) to 10 000 mPas (Brookfield, Spindle No. 4.10 rpm). 11. Homopolymer of diallylamine according to claim 9 in the form of the free polyamine base, its solution in water with a concentration of 20 wt .-% to 30 wt .-% a viscosity of 100 mPas (Brookfield, spindle No. 3,100 rpm) to 2000 mPas (Brookfield, Spindel, No. 4,100 rpm). 12. Use of a homopolymer according to any one of claims 9 to 11 for the aftertreatment of dyeings which are obtainable with dyes containing anionic groups on textile materials containing hydroxyl groups or nitrogen atoms, and / or for the treatment of said textile material before dyeing with subsequent dyeing with the dyes mentioned. 13. Use according to claim 11, characterized in that direct or reactive dyes are used for the coloring. 6